Signob to i



Patented Jan.

PATENT-OFFICE Q 1313153 161: nmnaa'r, or rnAxxron'r-oN-rnn-Main,rnsuizsi'ixiin,' GamnnzTas- 1 I s'ramnznn SOLUTIoNs or :smmm

m; mime Application flledlrebruaryfi i 1931, semi in." 518,802, and ineemny rebm as; 1920.

I present invention relates to stabilized J olutions. of iccatives.

' 3 S lutions of siccatlves in white spirit,'ben-' occur. or the. l l mthe nature. andthe quantity of the volatile turpentineor other volatilesolvents as a ,rule tend to exhibit sedimentation deposit) when allowedto" stand for some timej The manner in'which deposits zene, oil of formthey assume depends on solvent used, but according to'my observationsisdependent in the'first line on the kind and Quantity of' the metalcontainedin theksiccative and it is approximately proportion is themosdriers zinc driers and calcium driersi responding to the high metalcontent, the

tionalito, the capability of these metals of accelerating the dryingprocess. ,The formation of, sediments therefore difierscon'siderlably inthe various naphthenates, linoleates i ,andfresinates." The tendencyto-sedimentat "pronounced in the cobalt driers, next range themanganesednermlead tendency of sedimentation is greatest in thevnaphthenates and the smallest in the resinates, part cularly in themolten resinates. In a he process of scdimentin'g or gelatinizing of thesolu siccatlves in volatile solvents are forming only colloidal, "andnot molecular solutions.

These colloids, are of a lyophile nature; they are thus. inclined "toswell in the solvents.

In the caseof cobalt naphthenateyhaving a high content, of activesiccative metal, the transition from the sol-state into the gel-state isithe mofstrapidland extensive and'gelatiniz'ation ijthroughoilt the"entire mass is 1 offreqn ent occurrence." These sedimentations place,the consumer succeeds only exception-V the consumer; Oncevelatini'zation has taken :allv toredissolve by again heatingthe masswith-the liquid which remained. even when V eporary, re-dissolutions ofthe precipitates can:

be obtained. i

replenished tlieaddition of evaporated volatile solvent. "In spite ofthe aid of fresh solvent, no re-dissolution at allor only tem- I havenow ascertained that these incon products thereof, such as benzoic acid,car-J boxylic acids of the; benzene series, such as amino-benzoic acid,or the derivatives, such I as hippuric acid, .phthalic 'acid,,cinnamic Yacid, naphthoicacid.

Cor-

tions the siccatives behave in a 7 markedimanner as colloids, as ingeneral the of free fatty acids in boiled linseedoihor simillic acid;furthermore the aromatic carboxylic acids, the homologue: and.substitution The morethe siccatve'metals the, sbiu- 7 tion of. thesiccatives are capable of-accelerating vthe:drying-,process, thegreater-are. the proport1ons of,. ,the unsaturated fatty acids which,may advantageously be added to the Q solution. By, the. addition ofthese carbox-.

vylic acids the stability of the, colloidal solutions isconsiderablyincreased. which effect may clearly be seen inthe viscosityremaining'constant. t i

' There may,for instanc'e,;be used about the following quantities offree unsaturated may '30 acids calculated upon the solid drier;

Per cent -With pure cobalt driers., v "15- -20 With manganese-cobaltdriers.... j 10 15. With cobalt-zinc driers and cobaltlead driersi. .e3-5 in 'the case of naphthenates and 'linoleates the vupper limit andinlrtliecase of resinates the lower limit isthe mostadvanta'geous.

The solutions of "siccatives thus prepared may be stored for any lengthof'time without showing an sediments or "gelatinizations.

This surprising effect of the free fatty acids, for instance of thelinoleic acid, was no means to be foreseen, the more so as deposit--especially of the'driers containing lead and zinc, is caused already bysmall quantities ilar oils, containing said 'siccatives'. 10c

- siccatives or tlle solvents.

even completely inspissated solutions to reconvert into highly fluidcompletely homogeneous solutions, whichprocess takes place to someextent even at ordinary temperature. B the addition of benzoic acidgelatinized so utions can be re'converted into workable condition.

The free carboxylic acids may be added either during the preparation ofthe solid prior to dissolving same in volal For the urpose in questioneven small quantities 0 an aromatic carboxylic acid are alreadysuilicient for: preventing the mass from gelatinizin in the'cas'e ofbenzoic acid,

for instance, on y about per cent of the quantity of linoleic acidmentioned above need be added.- Larger quantities have, however, b nomeans a detrimental effect. By the ad ition ofbenzoic acid thecapability of the siccativesof accelerating the drying process is stillincreased compared with the addition of linoleic acid. 1 Theviscosity islikewise considerably reduced thereby. The viscos- Y ities of asiccative-withoutany of the above A of 1 volatile solvent (i. e. acontent 0 20 per cent troduced, while well stirring, into 385 kgs. of"

mentioned additional substances, of a siccative containing 20 per centof linoleic acid and of a siccative containing 5 per cent of benzoicacid stand in a proportion of about 5 :2 1. 4

In thefollowing examples the proportion art of the siccative to 4 artsof the of siccative) has been chosen as that which is the most used for.solutions of siccatives. The formation of precipitates is, however,

likewise not to be feared, if more diluted or. more concentratedsolutions are prepared.

The following examples serve to illustrate.

my invention, but they are not intended to .limit it thereto:

(1) 100 kgs. of solid cobalt naphthenate are gradually caused to melt ina. container at about 140 C. As soon 'asthe fused mass is completely.liquid, 380 kgs. of white spirit areadded in a thin stream, whilefurther vigorously stirring. 20 kgs. of linoleic acid. are

then run in and stirring is continued until a completely uniformsolution is obtained. In

orderto remedy the inflammability of solutions of this kind,one-quarterof the white spirit, or more, is suitably replaced by carbon bons.

(2) 100 kgs. of solidmanganese linoleate in pieces as small as possibleare gradually inoil of tar entine previously heated to a temperaturetwe'en'140 G. and 150 C. Stirring is continued until the solid drier hascompletely dissolved. After the solution has been allowed to. cool, anyoil of turpentine lost by volatilization is added again and in order toprevent the solution from gelatinizing, 15 kgs. of arachidic acid areintroduced, while stirring.

(3) 100 kgs. of solid cobalt-lead resinate are dissolved in the cold orat a moderate temperature in 400 kgs. ofa usual volatile sol-5 vent. 3kgs. of linoleic acid are then introduced, while stirring.

"(4) In a vessel-which can be tightl closed 275kgs. of a mixture ofhydrocar ons of the terpene series, 120'kgs. of benzene and 5 kgs. ofperillic acid are poured on kgs. of zinc naphthenate and 25 kgs. ofcobalt linoleate; the whole visstir'red or agitatedv from time to timeat ordinary temperature until the driers have completely dissolved whichwill occur after about 4 hours. The solution obtained will keep freefrom sedi mentation and has no tendency to gelatinize.

(5) About 400 kgs. of white spiritor of. another volatile solvent arerun in'a thin stream at about 130 0., while stirring, into kgs. ofprecipitated and washed cobalt naphthenate which have been dehydrated.When the temperature has fallen below 100 C., 6 kgs. of benzoic acid aregradually added and stirring is continued until the solution iscompletely uniform;

a (6) 100 kgs. of manganese linoleate are heated until a uniform melt isobtained. There are then introduced in the manner, as described inExample 1, 400 kgs. of san ajol (a fraction of petroleum hydrocarbonsoiling within the limits of 150 to 190 0.),

while simultaneously adding 5'kgs. of orthoamino benzoic acid.

(7 100 kgs. of cobalt-zinc resinate are dissolved by gently heating in400 kgs. of oil of turpentine, and 3 kgs. of phthalic acid are thenadded thereto.

, (8) 100 kgs. of cobalt-manganese naphthenate in small pieces areplaced in a vessel which can closed tight 3 kgs. of benzaldehyde and 3kgs. of ippurlc acid are added thereto and on the mixture there arepoured 900 k of a mixture of volatile by.-

drocarbons o the terpene series and agitat-" ed or intimately stirred atordinary temperae ture until the solid drier has completely dissolvedwhich can easily be attained in about M hours, as the aromaticcarboxylic acids capable of preventing'the gelat-inizationsimultaneously possess the peculiarity of pro- 'moting the dissolution.tetrachloride or other halogenated hydrocar- For sake of simplificationI have designed, in the following claims,-the solutions according tomyinvention, i. e. not depositing and 1 not' gelatinizing' solutions bythe term stabilized solutions. 7

I claim: v

1. As a new composition of matter, a stabilized solution consisting of asiccative, a volatile solvent and an organic carboxylic acid of thegroup consisting of aromatic carboxylic and unsaturated aliphatic acids.

2. As a new composition of matter, a stabilized solution consisting of asiccative, a volatile solvent and an unsaturated aliphatic carboxylicacid.

3. As a new composition of matter, a stabilized solution consisting of asiccative, a volatile solvent and linoleic acid.

l. As a new composition of matter. a sta-- bilized solution consistingofa siccative, a volatile solvent and an unsaturated organic carboxylicacid in a quantity ranging from 3 to 20 per cent of the siccative.

5. As a new composition of matter, a stabilized solution consisting of asiccative, a volatile solvent and an unsaturated aliphatic carboxylicacid in a quantity ranging from 3 to 20 per cent of the siccative. A

6. As a new composition ofmatter, a stabilized solution consisting of asiccative, a volatile solvent and linoleic acid in aquan'tity rangingfrom 3 to 20 per cent of the siccative. 4 v

7. As a new composition of matter, a stabilized solution consisting of asiccative a volatile solvent and an unsaturated aliphatic carboXylicacid in a quantity ,ranging from 15 to 20 per cent of the siccative.

8. As a new composition of matter, a

stabilized solution consisting of a siccative, a volatile solvent andl1n0le1c acid 1n. a, quantity ranging from 15 to 20 per cent of'thcsiccative.

9. As a new compos tion of matter, a stabilized solution consisting of asiccatlve, a

' volatile solvent and linoleic acid in a quantity of about 20 per centof the siccative.

10. As a new composition of matter, a stabilized'solution consisting ofa siccative, a volatile solvent and an aromatic carboxylic acid.

11. As a new composition of matter, asta bilized solution consisting ofa siccative, a volatile solvent and an aromatic carboxylic acid of thebenzene series.

12. As a new composition of matter, a stavolatile solvent and anaromatic oarboxylic acid of the benzene series in a quantity of about 6per cent of the siccative.

16. As a new composition of matter, a stabilized solution consisting ofa siccative, a

volatile solvent and benzoic acid in "a quantity of about 6 per cent ofthe siccative.

17. As a new composition of matter, a sta bilized volatile solvent andbenzoicacid in a quantity of about 6 per cent of the siccative.

18. As a newcomposition of matter, a stabilized solution consisting ofa'siccative, a volatile solvent and amino-benzoic acid in a quimtiitxyof about 5% of the siccative.

9. bilized solution consisting of a siccative. a volatile solvent'andphthalic acid in a quantity of about 3% of the siccative.

20. As anew composition of matter, a stabilized solution consisting of20 per cent of a siccative, an unsaturated carboxylic acid in a quantityran ing from 3 to 20 per cent of the siccative, t e balance being avolatile solvent.

In testimony whereof, I aflix my signature.

' FRIEDRICH MEIDERT.

bilized solution consisting of a siccative, a

volatile solvent and an aromatic carboxylic acid in a quantity rangingfrom 3 to 6'per cent of the siccative. I

13. As a new composition of matter, a stabilized solution consisting ofa siccative, a volatile solvent and an aromatic carboxylic acid of thebenzene series in a quantity ranging from 3 to 6 per cent of thesiccative.

14. Asa new composition of matter, a stabilized volatile solvent and anaromatic carboxylic acid in a quantity of about 6 per cent of thesiccative. I

15. As a new composition of matter, a stabilized solution consisting ofa siccative, a

solution'conslsting of a siccative, a

solution consisting of a siccative, a

so A s a new composition of matter, a sta-

